WO2007119812A1

WO2007119812A1 - Non-chromate rust-preventive surface treating agent for metallic member having zinc surface, and metallic member having zinc surface coated with the rust-preventive coating film

Info

Publication number: WO2007119812A1
Application number: PCT/JP2007/058137
Authority: WO
Inventors: Yasuhiko Endo; Hideaki Nogami; Shunjiro Watanabe; Shoichiro Adachi; Yukiyasu Kan
Original assignee: Hoden Seimitsu Kako Kenkyusho Co., Ltd.
Priority date: 2006-04-18
Filing date: 2007-04-13
Publication date: 2007-10-25
Also published as: KR20090013194A; US8623503B2; EP2009073A4; EP2009073A1; CN101426871A; US20130122238A1; US20090169875A1; US8367201B2; JP5566024B2; CN101426871B; JPWO2007119812A1; TWI411702B; TW200745380A; EP2009073B1; KR100983464B1

Abstract

Disclosed is a non-chromate rust-preventive surface treating agent which can form, on a zinc surface of a metal member, a silica-containing coating film which hardly causes cracking or detaching and can impart good anti-rust properties to the surface. The agent comprises a solution of an alkoxysilane oligomer having a weight average molecular weight of 1,000 to 10,000 in an alcohol, wherein 2.5 to 15% of silicon atoms in the alkoxysilane oligomer molecule are substituted by titanium atoms. The alkoxysilane oligomer which is partially substituted by titanium can be produced by reacting a titanium compound with a tetraalkoxysilane monomer or an alkoxysilane oligomer in an alcoholic solution, wherein the titanium compound can be prepared by chelating about half of alkoxide groups in titanium tetraalkoxide.

Description

Specification

Non-chromium antifouling surface treatment agent for metal parts having a zinc surface and metal parts having a zinc surface coated with the antifouling film

Technical field

[0001] The present invention relates to a non-chromium antifouling surface treatment agent used for preventing the occurrence of white glaze and red glaze in a metal member having a zinc surface such as a zinc-plated bolt or nut, and its fender The present invention relates to a metal member having a zinc surface coated with a skin film.

Background art

[0002] In Europe, RoHS regulations come into effect, and surface treatments containing hexavalent chromium components such as chromate treatment (surface treatment using hexavalent chromium components) applied to impart antifouling performance to zinc surfaces The use of the agent was regulated. Along with this, trivalent chromium surface treatment applied to zinc-plated metal members has become widespread in industry instead of chromate treatment. However, trivalent chromium surface treatment has several problems. For example, the renewal life of the liquid, which is difficult to manage the treatment liquid, is short V, and the coefficient of friction of the surface of the zinc-plated metal member treated with trivalent chromium is large. For some fastener members such as zinc bolts and nuts, it is necessary to further apply a surface treatment agent that adjusts the friction coefficient. In addition, the anti-corrosion performance of zinc-plated products with a trivalent chromium surface treatment is inferior to that of conventional chromate-treated products. The specification is also loosened.

[0003] Furthermore, it is inevitable that a part of trivalent chromium is changed to hexavalent chromium due to the equilibrium reaction, and a considerable amount of hexavalent chromium component is detected in the film. For this reason, the trivalent chromium surface treatment is a temporary surface treatment, and it is considered that it should move to a complete non-chromium surface treatment soon.

[0004] Many treatment methods have already been proposed for complete non-chromium surface treatment. However, the zinc-plated metal member with a non-chromium surface treatment that is as thin and coated as the chromate treatment has not reached the practical level. When top-coating is applied, a coating with a thickness of more than 10 μm is applied to the surface of a zinc-plated metal member with a non-chrome surface treatment. If required, the required fendering performance can be achieved. However, the non-chromium antifouling surface treatment for zinc-plated surfaces, which exhibits a fouling performance comparable to the chromate treatment with only a thin film, is currently other than the non-chromium antifouling surface treatment previously proposed by the present inventors. Is not found.

[0005] In Patent Document 1, the present inventors proposed a non-chromium surface treatment agent that forms a siliceous thin film that can be applied to the surface of a zinc-plated metal member to suppress the occurrence of red coral for a long time. did. The non-chromium surface treatment agent contains an effective amount of ultra-fine titanium oxide powder in which the average particle size of the dispersed primary particles is 70 nm or less.

[0006] In addition, in the Patent Document 2, the present inventors have proposed a non-chromium anti-fouling surface treating agent for zinc surface, which is mainly composed of an alcohol solution of an alkoxysilane oligomer having a specific weight average molecular weight. By applying the non-chromium antibacterial surface treatment agent to zinc surfaces such as zinc-plated products to form a thin siliceous film, it is possible to prevent the occurrence of white glaze for a long time.

[0007] The non-chromium surface treatment agent mainly composed of an alcohol solution of an alkoxysilane oligomer is an activation treatment (as a pretreatment for chromate treatment) in which a metal member is immersed in a dilute nitric acid solution after zinc plating. When applying non-chromium surface treatment, poor anti-fouling performance is often obtained. For this reason, a method of applying a non-chromium antibacterial surface treatment to a zinc-plated member that has been washed and dried without applying nitric acid activation treatment (vitaling) after zinc plating is adopted.

[0008] In addition, non-chromium anti-fouling surface treatment agent mainly composed of an alcohol solution of alkoxysilane oligomer V, whitening (without chromate treatment) zinc, which was also obtained by several manufacturers of zinc plating When applied to galvanized bolts, there was a problem that the antifouling performance against the occurrence of white glazing varied greatly depending on the zinc galvanized bolts of the galvanizing supplier.

[0009] As a method for avoiding this problem, the present inventors have disclosed in Patent Document 3 a non-chromium anti-mold surface treatment agent comprising a non-chromium chemical conversion treatment and an alcohol solution of an alkoxysilane oligomer as a main component. Proposal of anti-bacterial treatment to apply However, the surface treatment requires the addition of at least one treatment process, and does not meet the user's request that the surface treatment is performed with a simple process.

[0010] Thereafter, this non-chromium surface treatment agent is applied to a zinc-plated metal member such as a bolt. If the film is stored for about a year with the film attached, the film will crack, and in places where the film is applied a little thicker (more than 3 μm), the crack will continue to occur. The phenomenon of peeling of the film was observed, and there was a problem that white powder appeared on the zinc-plated surface and it appeared to have white glaze.

[0011] Although Patent Document 4 does not describe antifungal performance, a coating composition obtained by hydrolyzing an alkoxysilane by adding an acid catalyst and water and performing condensation polymerization while evaporating the alcohol and water is disclosed. It is disclosed. In the examples, the alkoxysilanes used as raw materials for the coating composition are all alkylalkoxysilanes. In addition, it is described that a chelate compound of zirconium, titanium or aluminum is blended in this composition. However, there is an example in which a zirconium chelate compound is blended in the examples (see Example 7 of the same document), but a coating on a metal member having a zinc surface is the same as the example in which an organic chelate titanium compound is blended. There was no example.

[0012] Patent Document 5 discloses a silica-based protective coating solution in which alkoxysilane and titanium alkoxide are subjected to condensation polymerization after hydrolysis in an alcohol solution using acetic acid as a catalyst. In this embodiment, CFRP (carbon fiber reinforced plastic) is exemplified as an object to be protectively coated in addition to metal parts such as titanium. In addition, alkoxysilane having an epoxy functional group and alkoxysilane having an amino group (indicating alkalinity) are used as the alkoxysilane used as a raw material for the protective coating solution. In the sol solution of alkoxysilane, the amino group functions as an alkaline catalyst that promotes the cross-linking reaction between oligomer molecules, so that the sol solution has a drawback that gelation easily occurs. In Example 4 of the same document (using a coating solution of a mixed solvent of alcohol and water), this protective coating solution is applied to a hot dip galvanized steel sheet, coated, and then applied to the coating film substrate. Evaluate the adhesion and check the strength and anti-fouling performance.

Patent Document 1: JP-A-2005-97719

Patent Document 2: JP 2005-264170 A

Patent Document 3: Japanese Unexamined Patent Publication No. 2006-225761

Patent Document 4: Japanese Patent Laid-Open No. 7-157715 Patent Document 5: Japanese Patent Laid-Open No. 2003-160759

Disclosure of the invention

Problems to be solved by the invention

[0013] The previously proposed non-chromium antifouling surface treatment agent mainly composed of an alcohol solution of an alkoxysilane oligomer has some problems. In particular, when a metal member galvanized under various different conditions is subjected to surface treatment with the previously proposed non-chromium antifouling surface treatment agent, satisfactory antifouling performance may not be obtained. Further, as moisture in the air was taken into the solution, a small amount of the dispersion-treated titanium oxide ultrafine powder blended to enhance the anti-mold performance tended to aggregate. When a coating was formed by applying a surface treatment agent containing agglomerated titanium oxide ultrafine powder to the zinc surface of the metal member, the surface became slightly whitish and white haze appeared to appear. In addition, as a phenomenon peculiar to coating films using the sol-gel method, when the applied film is dried and baked, tensile stress is generated in the coated film as the solvent evaporates, and this stress causes cracks in the film. . In the cracked part, if there was a little thick part in the film, it tended to peel off over time. When the film is peeled off, it appears as white powder and white dust appears on the surface of the metal member.

[0014] The present invention eliminates the problems of the previously proposed non-chromium antifouling surface treatment agent mainly composed of an alcohol solution of an alkoxysilane oligomer, and improves the antifouling performance. It aims at providing a processing agent.

[0015] That is, the present invention further improves the antifouling performance of the non-chromium antifouling surface treatment agent, and thus has a poor compatibility with a surface treatment agent that is difficult to impart practical antifungal performance. In addition to imparting a practical level of antifouling performance to the zinc-plated parts, cracks and peeling are unlikely to occur in the formed antifouling coating! Purpose.

Means for solving the problem

[0016] The non-chromium antifouling surface treating agent for metal members having a zinc surface according to the present invention is an alcohol solution of an alkoxysilane oligomer having a weight average molecular weight Mw of 1,000 to 10,000. Some of the key atoms are organic chelated titanium The total amount of titanium and titanium in the alcohol solution is substituted with titanium from the compound, and the alcohol solution contains 2.5 to 15 atomic percent titanium relative to the total amount of silicon and titanium. The amount is 5 to 20% by weight when converted to SiO and TiO respectively.

twenty two

The

[0017] Alcohol solution power of alkoxysilane oligomer Hydrolysis and condensation of alkoxysilane raw material and organic chelate titanium compound by adding acid catalyst and water to alcohol solution containing alkoxysilane raw material and organic chelate titanium compound A polymerized and synthesized product is preferred.

[0018] Alternatively, an alcohol solution of an alkoxysilane oligomer is synthesized by synthesizing an alkoxysilane oligomer by hydrolyzing and polycondensing the alkoxysilane raw material by adding an acid catalyst and water to an alcohol solution containing the alkoxysilane raw material. It can be a mixture of an oligomeric alcohol solution and an organic chelate titanium compound.

[0019] In the present invention, the organic chelate titanium compound is 40 to 40% of the alkoxy group of the titanium alkoxide.

60% is preferably blocked or substituted with a chelating agent.

[0020] In the present invention, the alkoxysilane alkoxysilane raw material of 90 to 99 mole ^_0/0 tetraalkoxysilane monomer or low molecular weight oligomer (weight average molecular weight Mw of tetraalkoxysilane used in the synthesis of oligomers 800 smaller. Low If heavy combined with the molecular weight oligomers, Ru seek mole ^_0/0 in a total molar amount of monomers.) it is preferred that the remainder is an alkyl alkoxy silane monomers.

[0021] In the present invention, the alkylalkoxysilane monomer cation trimethoxysilane, methyltriethoxysilane, etyltrimethoxysilane, vinyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane force are also at least one selected. It is preferable.

[0022] In the present invention, the chelating agent is preferably a 13-diketone or octylene glycol. As the β-diketone, acetylacetone is preferably used.

[0023] The alcohol solution of the alkoxysilane oligomer of the present invention preferably contains 0.1 to 2% by weight of an alcohol-soluble resin. It is preferred that the alcohol soluble in the alcohol is polybutyral.

[0024] The alcohol solution of the alkoxysilane oligomer of the present invention contains boric acid in the range of 0.004 to 0.10. U, preferred to include, by weight.

[0025] In the present invention, it is preferable that 20 to 40% by weight of the alcohol component in the alcoholic solution of the alkoxysilane oligomer is an alcohol or glycol ether having a boiling point of 97 ° C or higher.

[0026] Further, alcohol having a boiling point of 97 ° C or higher or glycol ether strength n-propyl alcohol (boiling point 97 ° C), n-butyl alcohol (boiling point 117 ° C), propylene glycol monomethyl ether (hereinafter referred to as “PGME”) Abbreviated, boiling point 121 ° C), sometimes referred to as ethylene dalcol monoethyl ether (both 136 ° C boiling point) and ethylene tert-butyl ether (hereinafter referred to as “ETB”, boiling point 152.5 ° C) And at least one selected from the group consisting of

[0027] The metal member of the present invention has a zinc surface coated with a siliceous film having an average thickness of 0.5 to 3 µm formed of the above-described non-chromium antifouling surface treatment agent.

[0028] It is preferable that the non-chromium antifouling surface treatment agent is applied to the zinc surface of the metal member by a dip-and-spin method to form a siliceous film. In addition, it is preferable that the siliceous film is baked at a temperature of 120 ° C. or less after coating.

[0029] In the present invention, a film containing silica as a main component, that is, a siliceous film, has a SiO component of 65%.

It means a film containing 2% by weight or more.

The invention's effect

[0030] With the non-chromium antifouling surface treatment agent of the present invention, the antifouling performance of the zinc surface coated with a siliceous film by substituting a part of the silicon in the alkoxysilane oligomer in the alcohol solution with titanium. In the salt spray test, the time until the occurrence of white glaze is increased to 210 hours or more, the time to occurrence of red glaze to 1150 hours or more, and the adhesion of the siliceous film to the zinc surface is improved. be able to.

[0031] By applying an alcohol solution of the non-chromium antifouling surface treatment agent according to the present invention to the zinc surface of a metal member to form a thin siliceous film of 0.5 to 3 m, the conventional chromate treatment and the inventors Whitening resistance superior to the non-chromium antifouling surface treatment agent mainly composed of the alcohol solution of the alkoxysilane oligomer previously proposed can be imparted to the dumbbell surface of the metal member. In addition, it suppresses the phenomenon of cracks in the siliceous film over time, and cracks occur. It is possible to prevent a phenomenon in which the liquor film peels off.

[0032] The siliceous film formed on the zinc surface of the metal member with the non-chromium antifouling surface treatment agent of the present invention is not affected by moisture in the air even if the film is scratched with a knife or the like. Self-healing property that prevents the occurrence of white glaze by covering the wound with a thin film by spreading the film components. BEST MODE FOR CARRYING OUT THE INVENTION

[0033] The alkoxysilane oligomer, which is the main active ingredient of the non-chromium antifouling surface treating agent according to the present invention, is an alkoxysilane oligomer in which a part of the oligomer in the oligomer molecule is substituted with titanium. Alternatively, a linear molecule having a molecular structure in which titanium and oxygen are alternately bonded and having a length exhibiting a good film forming property is formed.

[0034] If the weight average molecular weight Mw of this alkoxysilane oligomer molecule is too small, the film-forming property and the antifouling performance that can be imparted to the metal member are inferior, and if it is too large, the stability of the alcohol solution (meaning preservation, time After that, it becomes gelled and becomes unusable.) The alkoxysilane oligomer molecule must have a weight average molecular weight Mw of 1,000,000 to 10,000.

[0035] An alkoxysilane oligomer obtained by adding an acid catalyst and water to an alcoholic solution of an alkoxysilane raw material and hydrolyzing and condensing it is a linear molecule, and this linear molecule is a single linear molecule. Or it is presumed that it is either a ladder type linear shape. On the other hand, an alkoxysilane oligomer obtained by polycondensation using an alkaline catalyst in an alcohol solution tends to progress in the three-dimensional polycondensation of the oligomer, and is easily gelled, so that the storage stability of the alkoxysilane oligomer solution is poor.

[0036] A more preferred weight average molecular weight Mw of an alkoxysilane oligomer in which a part of the cage in the molecule is substituted with titanium is 1,500 to 5,000. In the present invention, the weight average molecular weight Mw of the alkoxysilane oligomer can be measured by gel permeation chromatography using a polystyrene standard using tetrahydrofuran as a solvent.

[0037] Good antifouling performance when a siliceous film is formed on the zinc surface of a metal member using a non-chromium antifouling surface treatment agent with alcohol solution in which part of the silicon in the alkoxysilane oligomer molecule is replaced with titanium Even if the siliceous film is thinner than 1 μm, it is possible to impart practical antifouling performance to a metal member having a zinc surface. Cracking or peeling occurs on the film In order to prevent this, it is effective to make the siliceous film thinner.

[0038] Further, the siliceous film formed by applying an alcohol solution of an alkoxysilane oligomer in which a part of the silicon in the molecule is substituted with titanium to the dumbbell surface of the metal member has excellent adhesion to the zinc surface. Even if the siliceous film is cracked, the siliceous film does not peel off.

[0039] The degree of the antifouling performance that the siliceous film formed with the non-chromium antifouling surface treatment agent in which a part of the silicon in the alkoxysilane oligomer molecule is substituted with titanium is imparted to the metal member having the zinc surface. If the ratio of substitution of titanium with titanium is small and too small, the cost will be high for the performance to be obtained, so the substitution ratio is preferably 2.5 to 15 atomic%. A more preferable replacement ratio of titanium in the alkoxysilane oligomer molecule with titanium is 3 to 10 atomic%.

[0040] The alkoxysilane oligomer in which a part of the cage is substituted with titanium is hydrolyzed and polycondensed by adding a small amount of acid catalyst such as hydrochloric acid and water to an alcohol solution containing the alkoxysilane raw material and titanium alkoxide. Can be synthesized. However, because the active titanium alkoxide is rapidly hydrolyzed, a precipitate is formed. Therefore, before mixing titanium alkoxide with an alkoxysilane raw material in an alcohol solvent and subjecting it to condensation polymerization, 40-60% of the alkoxy group of the titanium alkoxide is removed. It is preferable to block or substitute with a chelating agent to reduce the reaction activity of the titanium alkoxide! /.

[0041] Titanium tetraalkoxide is preferably used as the titanium alkoxide. Titanium tetraisopropoxide and titanium tetra _n -butoxide can be used as titanium tetraalkoxide. J8-diketones such as acetylethylacetone and octylenedarcol can be used as chelating agents to block or substitute alkoxy groups. Since acetylacetone reacts with the zinc surface and wears out the zinc layer, the non-chromium antifouling surface treatment agent of the present invention and tantalene glycol, which has a low reactivity with the dumbbell surface, are used as the chelating agent for the titanium alkoxide. Is preferred.

[0042] The non-chromium antifouling surface treatment agent of the present invention is an alkoxysilane monomer or a low molecular weight oligomer thereof (weight average molecular weight Mw is smaller than 800. In the case of an oligomer, it is polymerized! /, The total molar amount of the monomer. To obtain the mol%.)) Is used as the alkoxysilane raw material. Hydrolysis is performed by adding an acid catalyst such as hydrochloric acid to the alcoholic solution of the above, and polycondensation is performed to obtain a linear molecular alkoxysilane oligomer having a required weight average molecular weight. In addition to mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid, organic acids such as acetic acid can be used as the acid catalyst.

[0043] Instead, an alcohol solution of an alkoxysilane oligomer that has been condensation-polymerized using an acid catalyst so as to have a required weight average molecular weight is prepared in advance, and then an alcohol solution of an organic chelate titanium compound is mixed with this solution. Then, the organic chelate titanium compound can be reacted with an alkoxysilane oligomer to prepare a non-chromium antifouling surface treatment agent.

[0044] When an alcohol solution of an organic chelate titanium compound is mixed later with an alcohol solution of an alkoxysilane oligomer having a required weight average molecular weight Mw, an alkoxysilane oligomer in which the molecules of the organic chelate titanium compound are addition-polymerized to the alkoxysilane oligomer is obtained. can get.

[0045] A solution obtained by mixing an alcohol solution of a titanium alkoxide chelated with octylene glycol with an alcohol solution of an alkoxysilane monomer or an alkoxysilane oligomer is obtained by mixing an alcohol solution of titanium alkoxide chelated with acetylylacetone. Compared to a solution mixed with an alcohol solution of an alkoxysilane oligomer, yellow coloration is less.

[0046] In the non-chromium antifouling surface treatment agent of the present invention, an alkoxysilane containing a titanium component is used to form a siliceous film having a thickness that provides a practical level of antifouling performance on the zinc surface of a metal member. The total amount of silicon and titanium in the oligomeric alcohol solution is 5 to 20% by weight when converting silicon and titanium to SiO and TiO, respectively. With key

twenty two

A more preferred total amount with titanium is 7 to 15% by weight.

[0047] The weight average molecular weight Mw of the alkoxysilane oligomer is large. On the other hand, a siliceous film with excellent antifouling performance can be formed, and the film does not easily crack, so that the preservation property of the antifouling surface treatment solution is not impaired. It is preferable to make it larger. Specifically, the polycondensation is performed so that the weight average molecular weight of the alkoxysilane oligomer is Mw force S1, 000 to 10,000, preferably 1,500 to 5,000.

[0048] Such an alkoxysilane oligomer can be synthesized by adjusting an alcohol solution mixed with starting materials to around pH4. The progress of the condensation polymerization reaction becomes saturated in a short time. Thus, it is preferable to synthesize the alkoxysilane oligomer while keeping the temperature of the alcohol solution at 35 ° C to 45 ° C. If the polycondensation reaction is saturated, the progress of the polycondensation reaction during the storage of the alcohol solution of the alkoxysilane oligomer at room temperature is slow, so the preservability of the alcohol solution of the alkoxysilane oligomer is good.

[0049] An organic component can be introduced into the alkoxysilane oligomer by copolymerizing a silane coupling agent, which is an alkylalkoxysilane having an organic group such as an alkyl group, with a tetraalkoxysilane monomer or a low molecular weight alkoxysilane oligomer. Moreover, an organic component soluble in alcohol can be dissolved in an alcoholic solution of an alkoxysilane oligomer and an organic component can be introduced into the siliceous film.

[0050] As the alkoxysilane raw material, it is preferable to use tetraethoxysilane, tetramethoxysilane, or a low molecular weight alkoxysilane oligomer obtained by condensation polymerization of these monomers. Sold as a low molecular weight alkoxysilane oligomer! /, Ruetyl silicate 40 (Mw = 745 pentamer)! / ヽ can use methyl silicate 51 (Mw 470 tetramer)! /.

[0051] In addition, the chelating agent used to suppress the reaction activity of the titanium alkoxide remains in the alcohol solution of the alkoxysilane oligomer after synthesis, and the coating of the antifouling surface treatment agent is performed at a temperature around 100 ° C. It is estimated that it remains in the siliceous film even after being baked on the zinc surface and plays a part in the softening of the formed siliceous film.

[0052] When a chelating agent in an amount exceeding 2 moles per 1 mole of titanium alkoxide is blended, most of the chelating agents in excess of 2 moles due to steric hindrance are not used for the formation of organic chelating titanium compounds. As a chelating agent used for titanium alkoxide, it is preferable to use j8-diketone such as acetylylacetone or octylene glycol.

[0053] When acetylacetone is added excessively, the boiling point of acetylosylacetone is as high as 140 ° C, so it is contained in the alcohol solution as a high boiling point solvent. Since octylene glycol is a high-boiling solvent above 240 ° C, it functions as a high-boiling point solvent in an alcohol solution like acetylenic acetone.

[0054] When an alkyl alkoxysilane monomer is introduced into an alkoxysilane oligomer with an organic group directly bonded to the silicon, the alcohol in a state in which the organic group is bonded to a part of the silicon is introduced. Becomes a xysilane oligomer. Due to the presence of the organic group bonded to the silicon, the siliceous film formed on the surface of the metal member can be softened, and the effect of suppressing the occurrence of cracks in the film can be obtained. As the alkylalkoxysilane monomer, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane, which have a low tendency to deteriorate the antifungal performance, are also selected. I prefer to pick at least one. In particular, butyltrimethoxysilane is preferred as an alkylalkoxysilane monomer.

[0055] However, if too many organic groups are introduced, the antifouling performance obtained when the siliceous film is coated on the zinc surface tends to be reduced. It is preferable to synthesize an alkoxysilane oligomer by blending at a ratio of 10 mol%, further 2-8 mol%.

[0056] Further, in the siliceous film formed by dissolving the alcohol soluble in alcohol in an alcohol solution of a non-chromium antifouling surface treatment agent and applying the antifouling surface treatment agent to the zinc surface of the metal member The rosin component can be introduced into the. When a rosin component is introduced into the siliceous film, it is possible to suppress the generation of cracks in the film by softening the film. If the organic resin soluble in alcohol is water-soluble, the water resistance of the formed siliceous film is impaired. Therefore, it is preferable to select a resin that is soluble in alcohol but not water.

[0057] Polyuraptilal resin is preferred as a resin suitable for this purpose. It is preferable that the amount of polybutybutyral resin dissolved in the alcohol solution of the non-chromic anti-bacterial surface treatment agent is 0.1 to 2% by weight, more preferably 0.2 to 1% by weight.

[0058] In addition to an organic resin such as polyvinyl butyral resin, if a small amount of boric acid is dissolved in an alcohol solution of a non-chromium antifouling surface treatment agent, there is an effect of suppressing the occurrence of cracks. It is preferable that 0.004 to 0.10% by weight of boric acid is dissolved in the alcohol solution.

[0059] In the dip-and-spin method, a metal member having a zinc surface is immersed in an alcohol solution of a non-chromium antifouling surface treatment agent, and the wet metal member is taken out of the alcohol solution and placed in a metal cage attached to a centrifuge. This is an application that sprinkles off the excess alcohol solution of the surface treatment agent attached to the surface of the metal member by centrifugal force. The metal parts covered with a thin liquid film (coating film) taken out from the bowl are baked at about 100 ° C after drying and Use a strong film.

[0060] The coating thickness of the antifouling surface treatment agent formed on the zinc surface of the metal member by the dip-and-spin method is not limited to the magnitude of the centrifugal force trapped on the metal member, and the alkoxysilane oligomer in the alcohol solution Affected by the concentration of alcohol and the viscosity of the alcohol solution. Since the siliceous film formed with a thick siliceous film tends to crack, the consumption of the antifouling surface treatment liquid increases and the cost of the surface treatment increases, so that the siliceous film requires a siliceous film. It is preferable to make it thin as long as the performance is satisfied.

[0061] The thickness of the siliceous film formed on the surface of the metal member is changed according to the purpose of use, but if it is less than 0.5 / zm, it is difficult to provide practical antifungal performance. It is preferable that the siliceous film formed on the zinc surface has an average thickness of 0.5 to 3 and ζ ΐη so that practical antifouling performance can be exhibited. A thin siliceous film with an average thickness is less prone to cracking and peeling, but it has poor antifungal performance. On the other hand, if the siliceous film is thick, cracks are likely to occur, so an average thickness of 0.7 to 2 m is more preferable.

[0062] The film thickness of the antifouling surface treatment agent coating film formed on the surface of the metal member is changed by changing the alcohol solution concentration of the non-chromium antifouling surface treatment agent and changing the number of revolutions when applied by the dip-and-spin method. The viscosity of the solution of the non-chromium antifouling surface treatment agent can be adjusted by changing the addition amount of the resin component having a thickening effect.

[0063] The dip-and-spin method is suitable for applying a solution of the anti-fouling surface treatment agent to a metal member having a small size such as a bolt or a nut. In addition, an alcohol solution of a non-chromium antifouling surface treatment agent can be applied in accordance with the size and shape of the product to be applied, in addition to the dip-and-spin method, the dip drain method, spray method, brush coating, etc. .

[0064] When applying by the dip drain method or spray method, it is preferable to change the concentration of the alcohol solution of the non-chromium antifouling surface treatment agent according to the method of applying to the metal member. I prefer to do it.

[0065] The alcohol used as the solvent for the non-chromium antifouling surface treatment agent maintains a concentration suitable for coating because the alcohol with a low boiling point alone increases the concentration of the solution when the alcohol evaporates quickly when the room temperature is high. Refill with alcohol as needed.

[0066] In addition, the humidity is high, such as on rainy days, and a non-chromium antifouling surface treatment agent is applied to the surface of a metal member indoors. When applied, condensation may occur on the surface, and the applied non-chromium anti-fouling surface treatment coating may be altered to reduce the anti-fouling performance of the silica coating.

[0067] In order to reduce condensation of alcohol by reducing evaporation of alcohol, it is preferable that 20 to 40% by weight of the alcohol component in the alcohol solution is alcohol having a boiling point of 97 ° C or higher or glycol ether in summer.

[0068] Alcohol having a boiling point of 97 ° C or higher is incorporated in the solution of the non-chromium antifouling surface treatment agent! / ヽ is n-propyl alcohol, n-butyl alcohol, PGME, ethylene glycol monoethyl ether, You can use ETB. In particular, ETB has a tendency to impair the antifouling performance of the siliceous film formed by condensation on the surface of the coating film to be formed when the humidity of the working atmosphere in which the liquid for the surface treating agent is applied is high! It is a preferred solvent with an inhibitory effect.

[0069] Since the formation of a non-chromium anti-fouling surface treatment agent coating on the zinc surface of a metal member having a small size is easy to form on the surface of a large number of metal members at once, the dip-and-spin method described above is used. Preferred to apply ,.

[0070] It is preferable that the coating film of the applied antifouling surface treating agent solution is dried and maintained at a temperature of 120 ° C or lower and baked to form a siliceous film. Since the user prefers a low baking temperature, it can be dried and cured at room temperature, but the protective performance that can be imparted at 80 ° C or below is slightly inferior. It is preferable to form the siliceous film by baking at 90 to 110 ° C. so that a siliceous film having good antifouling performance can be efficiently formed in a short time on the surface of the metal member. The heating time for baking the anticorrosive film at 90 to 110 ° C is preferably 10 to 25 minutes.

[0071] The zinc surface in the present invention can be an alloy containing zinc as a main component, and the non-chromium antifouling surface treatment agent of the present invention can be applied to a metal member to which various dumbbells are applied, dumbbell die-cast member. It can be preferably applied.

Example

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

[0073] Synthesis of alkoxysilane oligomer

Titanium tetraisopropoxide (Matsumoto Fine Chemical Co., Ltd.), a titanium alkoxide TA-10) 2) 55.5 parts by weight are mixed with 60 parts by weight of isopropyl alcohol and 18 parts by weight of acetylethylacetone, and about half of the hydrolyzable isopropoxy group of titanium tetraisopropoxide is added with a chelating agent. A blocked solution (yellow color) was obtained.

[0074] Next, as an alkoxysilane raw material, ethyl silicate 40 (product of Tama Chemical Industry Co., Ltd., an approximately pentameric oligomer obtained by polycondensation of tetraethoxysilane;

2

Contains 0% by weight. ) 250 parts by weight, vinyltrimethoxysilane (SH6300 manufactured by Toray Dow Co., Ltd.) and a mixture of about 65 parts by weight of isopropyl alcohol were mixed with the isopropoxy group of titanium tetraisopropoxide obtained above. A solution in which about half of the solution was blocked with the chelating agent acetylacetone was mixed. To this solution was added acidic water mixed with 5.5 parts by weight of 1N hydrochloric acid and 27.9 parts by weight of water, and the mixture was subjected to polycondensation by stirring at 35 ° C for 24 hours with stirring. The alkoxysilane oligomer solution A shown was obtained. Of alkoxysilane raw materials used in the alkoxy silane oligomer solution A 9. 2 mol ^_0/0 (in this case, E chill Silicate 40 was calculated as a monomer. Hereinafter the same.) Was alkylalkoxy Sila Nmonoma.

[0075] Here, the alkoxysilane oligomer solution A obtained are substitution with titanium 4.7 atomic ^_0/0 of Kei element, the total content in terms of Kei element and titanium SiO and TiO are 24.6 % By weight

twenty two

there were. The weight average molecular weight of this alkoxysilane oligomer was measured using a gel permeation chromatography (HLC-8120GPC from Tosoichi Co., Ltd.) (using tetrahydrofuran as the solvent and polystyrene as the standard). It was.

[0076] Similarly, the composition of the formulation described in column B of Table 1 was reduced by reducing the blending amount of butyltrimethoxysilane, and kept at 35 ° C for 24 hours while being stirred for condensation polymerization to obtain an alkoxysilane oligomer. solution B (degree of substitution Kei element by titanium 5 atomic ^_0/0, SiO and TiO and Kei-containing and titanium

Combined content in terms of 2 2 was 21.8 wt ^_0/0. ) In alkoxysilane 2 mole ^_0/0 alkyl alkoxy silane monomer of the alkoxysilane raw material use was the oligomer first solution B, about the § isethionate Honoré acetone lifting one isopropoxy titanium tetraisopropoxide using chelating agents It was the amount to block half. The weight average molecular weight of this alkoxysilane oligomer was 2270.

[0077] Next, an excess of acetylosylacetone (the isoprop of titanium tetraisopropoxide used) Acetylacetone, 1.5 times the amount of the poxy group, was added. ) And the composition of the formulation shown in column C of Table 1 was stirred for 24 hours at 35 ° C while agitating, and was subjected to polycondensation to give a yellow colored alkoxysilane oligomer solution C (replacement rate of titanium with titanium) is 6. 6 atoms ^_0/0, the total content in terms of Si O and TiO got 21. was 4 wt%.). Alkoxysila

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2 mole ^_0/0 of the alkoxysilane raw materials formulated to down oligomer solution C was alkylalkoxy silane monomer. The weight average molecular weight of this alkoxysilane oligomer was 1760.

[0078] In addition, gamma as alkyl alkoxy silane monomer - use a butyl alcohol solvent - with methacryloxypropyl trimethoxysilane (SH6030) of the entire alkoxysilane raw material 16.7 mole ^_0/0, in place of isopropyl § alcohol _η The composition described in column D of Table 1 prepared in this manner was subjected to polycondensation by stirring at 35 ° C for 24 hours while stirring, to obtain an alkoxysilane oligomer solution D (the substitution rate of titanium with titanium was 14.3%). In the case of silicon and titanium, SiO and TiO

The total content converted to 2 was 23.4% by weight. ) The case used here

2

The amount of tylacetone was equivalent to 25% of the isopropoxy group of titanium tetraisopropoxide. The alkoxysilane oligomer had a weight average molecular weight of 1720.

[0079] In addition, titanium tetra-n-butoxide was used instead of titanium tetraisopropoxide, and the composition described in column E of Table 1 was subjected to condensation polymerization by stirring at 35 ° C for 24 hours while stirring. oligomer solution E (the substitution rate of Kei element by titanium at 12.2 atomic ^_0/0, the total content in terms of Kei element and titanium SiO and TiO was 18.7 wt%.) was obtained. In addition

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The alkoxysilane oligomer solution E was not added with an alkylalkoxysilane monomer. The amount of the acetylating agent acetylylacetone used was equivalent to 33% of the n-butoxy group of titanium tetra n-butoxide. The alkoxysilane oligomer had a weight average molecular weight of 1910.

[0080] Also, methyl triethoxysilane (SZ6383 manufactured by Toray Dow Co., Ltd.) as an alkylalkoxysilane monomer was prepared by using 8.0 mol% of the total alkoxysilane raw material, and is shown in column F of Table 1. composition by condensation polymerization was kept for 24 hours in 35 ° C with stirring, substitution rate of Kei element according alkoxide silane oligomer solution F (titanium 4. 9 atomic ^_0/0, Keimoto The total content of titanium and titanium converted to SiO and TiO was 22.7% by weight. ) Na

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Acetylacetone used here was an amount corresponding to 42% of the isopropoxy group of titanium isopropoxide. The alkoxysilane oligomer had a weight average molecular weight of 1990.

[0081] Next, an alkoxysilane oligomer solution prepared by mixing the composition described in column G of Table 1 prepared without blending an alkylalkoxysilane monomer or titanium alkoxide with stirring at 35 ° C for 24 hours, followed by condensation polymerization. G (content of conversion of silicon to SiO was 20 weight ⁰ /.

2

. ) The alkoxysilane oligomer had a weight average molecular weight of 2310.

[0082] Further, as described in column H of Table 1, 2 mol% of butyltrimethoxysilane was mixed with an alcohol solution of ethyl silicate 40 in the total amount of the alkoxysilane raw material, and a composition having a composition not containing titanium alkoxide was stirred. While maintaining the temperature at 40 ° C for 20 hours for condensation polymerization, the alkoxysilane oligomer solution H (contains no titanium component;

2

2% by weight. ) The alkoxysilane oligomer had a weight average molecular weight of 2004.

[0083] Next, as described in column I of Table 1, the amount of vinyltrimethoxysilane was increased to 9.1 mol% of the total alkoxysilane raw material, and the composition of the formulation not containing titanium alkoxide was stirred. It was kept at 40 ° C. for 20 hours and subjected to condensation polymerization to obtain an alkoxysilane oligomer solution 1 (containing no titanium component, and content obtained by converting silicon to SiO was 19.3% by weight).

2

It was. The alkoxysilane oligomer had a weight average molecular weight of 2020.

[0084] As shown in column J of Table 1, a composition prepared by adding vinyltrimethoxysilane, 1N hydrochloric acid and water to 250 parts by weight of ethyl silicate 40 at 35 ° C for 24 hours The alkoxysilane oligomer was synthesized by keeping warm. After synthesis, the alcohol solution of the alkoxysilane oligomer was stored in a sealed state for about 2 years and 6 months, and the weight average molecular weight of the alkoxysilane oligomer in the alcohol solution was measured to be 7820. Since the weight average molecular weight of the alkoxysilane oligomer immediately after synthesis is usually around 2,000, it was understood that the condensation polymerization further progressed during storage.

[0085] [Table 1]

0 Ethyl silicate 40: Low molecular weight tetraethoxysilane oligomer (Tammer, SiO ₂ equivalent content: about 40 wt <½) manufactured by Tama Chemical Co., Ltd.

O alkylalkoxysilane (mol%): mol% of alkylalkoxysilane in the alkoxysilane compound in terms of monomer.

Since ethyl silicate ⁴⁰ is a pentamer of 亍 traethoxysilane, 1 mol (744.5) was calculated as 5 mol.

OSH6300: Silane coupling agent (vinyltrimethoxysilane) manufactured by Toray Dow Corning (Mw: 148.2)

OSH6030: Toray 'Dacon Co., Ltd. silane coupling agent-methacryloxypropylmethoxysilane) (Mw: 248)

OSZ6383: Methyltriethoxysilane (Mw: 178) manufactured by Toray Dow Corning Co., Ltd.

OTA-10: Titanium tetraisopropoxide manufactured by Matsumoto Fine Chemical Co., Ltd. (Mw: 283.8)

OTA-25: Titanium tetra n_butoxide (Mw: 339.9) manufactured by Matsumoto Fine Chemical Co., Ltd.

[0086] Example 1

In 48 parts by weight of alkoxysilane oligomer solution A, 7.5 parts by weight of a 10% by weight butyl acetate solution of polybutyral, 1 part by weight of a 0.6% by weight isopropyl alcohol solution of boric acid, and isopropyl alcohol are added. 44.5 parts by weight were mixed to obtain an alcohol solution of the non-chromium antifouling surface treating agent of Example 1 shown in Table 2-1. The combined content of silicon and titanium in this non-chromium surface treatment solution converted to SiO and TiO is 11.7 wt.

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%Met.

[0087] Next, the non-chromium of Example 1 in which five M8 bolts (half screw with a neck length of 45 mm) plated with zinc in a zincate bath (plating thickness: 5 to 7 μm) were placed in a container. Put it in the anti-bacterial surface treatment solution and rotate it. Remove the 5 bolts from the container and place them in a stainless steel jar attached to the centrifuge, and rotate the jar at 700 RPM (rotation radius approx. 150 mm) for 4 seconds. The excess antifouling surface treatment solution adhering to the surface of the M8 bolt was shaken off. Next, the bolts wetted with the antibacterial surface treatment agent were placed on a stainless steel wire mesh, placed in a baking furnace, dried at 60 ° C for 10 minutes, heated to 100 ° C, held for 15 minutes, and baked. One of the M8 bolts of Example 1 coated with a coating of a non-chromium antifouling surface treatment agent was observed with a stereomicroscope (magnification approximately 40 times) to check for cracks. Put the remaining 4 M8 bolts into a salt spray tester (SST) based on JIS-Z-2371, remove one after 24 hours, wash with water, dry and bolt with a stereomicroscope (a magnification of about 40 times) The surface of the film was observed for the presence or absence of cracks in the antifouling film. The remaining three bolts were placed in a salt spray test machine as they were, and when the surface of the bolt was observed with the naked eye every 24 hours, the time when white glaze occurred and the time when red glaze occurred were recorded.

[0088] The time of occurrence of the white glaze and red glaze shown in Table 2-1, Table 2-2 and Table 3 is the time when white glaze or red glaze was observed in two of the three.

[0089] The bolt coated with the siliceous film of the non-chromium antifouling surface treatment agent of Example 1 had good antifouling performance against the occurrence of white glazes and red glazes that were difficult to crack. In addition, when the bolts observed with a stereomicroscope were buried in the resin, a cut sample was made, and when the cross section of the bolt was observed with a microscope to examine the film thickness of the siliceous film, the average film thickness was slightly weaker than m. . For Examples 2 to 19 and Comparative Examples 1 to 3, the film thickness was examined in the same manner, and as a result, the average film thickness of Comparative Example 1 was 2.3 m. Silica coating The average film thickness of each film was 0.7-2 / ζ πι.

[0090] Eight bolts covered with a siliceous coating of non-chromium antifouling surface treatment agent were taken out from the salt spray tester 24 hours later, washed with water and dried to observe the presence or absence of cracks in the coating. This is a kind of accelerated test that causes cracks in the siliceous film, and the cracks occurred in the fouling film after leaving the 8 bolts covered with the siliceous film of the non-chromic antifouling surface treatment for a long time. This is an alternative to examining power.

[0091] Example 2

52. 8 parts by weight of alkoxysilane oligomer solution In addition to 10% by weight polybutylbutyral solvate solution, 0.6% by weight isopropyl alcohol solution of boric acid, and isopropyl alcohol in the formulation shown in Table 2-1. By mixing, the non-chromium antifouling surface treatment agent of Example 2 was obtained.

[0092] Example 3

48. against the alkoxysilane oligomer solution Β of 0 parts by weight, 10 weight ^_0/0 Echiruse port cellosolve solution 3 parts by weight of poly Bulle butyral, 0.6 weight ^_0/0 isopropyl alcohol solution 5 parts by weight of boric acid And 38 parts by weight of isopropyl alcohol were mixed to obtain the non-chromium anti-mold surface treatment agent of Example 3.

[0093] Next, in the same manner as in Example 1, 5 volt 8 bolts (half screw with a neck length of 45 mm) were applied to each of Examples 2 and 3 by the dip and spin method. It was applied and baked in the same manner as in Example 1. Each one was examined for cracks with a stereomicroscope, and the remaining 4 were placed in a salt spray tester. After 24 hours, each one was taken out and washed with water. The presence or absence was examined, and the results are shown in Table 2-1. In addition, for each of the three bolts placed in the salt spray tester, the presence or absence of white sharks and red foxes was examined with the naked eye every 24 hours. The allowed times are shown in Table 2-1.

[0094] Both the crack resistance and the antifungal performance of Example 2 and Example 3 are good, and they are taken out in a salt spray tester for 24 hours and taken out. The cracks observed in the film were minor and had no practical problem!

[0095] Examples 4 to 6 Using the alkoxysilane oligomer solution B, the non-chromium antifouling surface treatment agents of Examples 4 to 6 were prepared with the composition shown in Table 2-1. In Examples 4 to 6, the boiling point is low and it is easy to evaporate, and a part of isopropyl alcohol is replaced with a high boiling point! 4-The non-chromium anti-mold surface treatment agent of Example 6 was prepared. Using these non-chromium antifouling surface treatment agents, they were applied to M8 bolts by the dip and spin method in the same manner as in Example 1, dried and baked. These bolts were examined for crack resistance and antifouling performance in the same manner as in Example 1. The results were as shown in Table 2-1, and all were good. In addition, by adding an alcohol solvent with a high boiling point, the alcohol solution power of the non-chromium anti-fouling surface treatment agent can be slowed to evaporate, and the fouling surface treatment agent can be applied to metal parts in summer when the temperature is high. Also when applied to the surface, the replenishment amount of alcohol evaporated from the antifouling surface treatment solution was reduced.

[0096] Example 7

Using the alkoxysilane oligomer solution C synthesized by adding an excess of the chelating agent acetylylacetone, the non-chromium antifouling surface treatment agent of Example ⁷ was prepared with the composition shown in Table 2-1. This non-chromium antibacterial surface treatment solution was applied by dipping and spinning to five M8 bolts plated with zinc in a zincate bath in the same manner as in Example 1, dried and baked. For these bolts, crack resistance and anti-fouling performance were examined in the same manner as in Example 1. As shown in Table 2-1, excessive force acetylacetone was added in each case. The effect of was unrecognizable.

[0097] Example 8

Using an alkoxysilane oligomer solution D synthesized by adding γ-metataloxypropyltrimethoxysilane instead of butyltrimethoxysilane as an alkylalkoxysilane monomer, the formulation composition shown in Table 2-1 was used. A chromium antifungal surface treatment agent was prepared. Next, in the same manner as in Example 1, this non-chromium antifouling surface treatment agent was applied by dipping and spinning to five 8 bolts that were zinc-plated in a zincate bath, dried and baked. These bolts were examined for crack resistance and anti-fouling performance in the same manner as in Example 1. As shown in Table 2-1, the anti-fouling siliceous material had a soft anti-fouling coating and no cracks. Get a film Although it was able to, it was a little inferior in anti-fouling performance!

[0098] Example 9

Using the alkoxysilane oligomer solution E containing titanium tetra-n-butoxide as the titanium alkoxide without the addition of an alkylalkoxysilane monomer, the nonchromium antibacterial surface treatment of Example 9 with the composition shown in Table 2-1 An agent was prepared. Next, this non-chromium anti-surface treatment agent was applied by dipping and spinning to five M8 bolts that were galvanized in a zincate bath in the same manner as in Example 1, dried, held at 100 ° C for 15 minutes, and baked. It was. These bolts were examined for crack resistance and antifouling performance in the same manner as in Example 1. As a result, as shown in Table 2-1, they were all good.

[0099] Example 10

Using an alkoxysilane oligomer solution F obtained by condensation polymerization of methyltriethoxysilane using titanium tetraisopropoxide chelated with acetylacetone, a part of the alcohol in the alcohol solution has a boiling point of 121 ° C. PGME was blended, and the non-chromium anti-mold surface treatment agent of Example 10 was prepared with the blending composition shown in Table 2-1. Next, in the same manner as in Example 1, this non-chromium antifouling surface treatment agent was applied to five M8 bolts zinc-plated in a zincate bath by the dive and spin method, and after drying, kept at 100 ° C for 15 minutes. I baked it. These bolts were examined for crack resistance and anti-fouling performance in the same manner as in Example 1. As shown in Table 2-1, they were all good.

[0100] Example 11

Do include titanium component obtained by polycondensation by blending Bulle trimethoxysilane, 52.8 alkoxysilane oligomer solution H of parts, 3 parts by weight of 10 weight ^_0/0 Echiru cellosolve solution of poly Bulle butyral, boric acid 5 parts by weight of a 1.2% by weight isopropyl alcohol solution, 23.8 parts by weight of isopropyl alcohol, a titanium otatilene glycol chelate compound made by Nippon Soda Co., Ltd. (compound whose alkoxy group is isopropoxide. , "TO

G ". 5.4 parts by weight), 10 parts by weight of PGME, and 15 parts by weight of ETB were mixed to prepare the non-chromium antifouling surface treatment agent of Example 11 shown in Table 2-2. The combination of silicon and titanium in the non-chromium surface treatment solution converted to SiO and TiO.

twenty two

The calculated content is 9.9% by weight, and the content ratio of titanium to the total amount of silicon and titanium is 4%. 6 atomic percent.

[0101] Next, this non-chromium surface treatment agent was applied to five M8 bolts zinc-plated in a zincate bath by a dip-and-spin method, dried and held at 100 ° C for 20 minutes for baking. These bolts were examined for crack resistance and fender resistance as in Example 1, and as a result, as shown in Table 2-2, both were good.

[0102] Example 12

Using an alkoxysilane oligomer solution I that does not contain a titanium component that has been polycondensed by increasing the blending ratio of butyltrimethoxysilane, the same composition as in Example 11 was used, and the non-conducting composition of Example 12 was used. A chromium antifungal surface treatment agent was prepared. The total content of silicon and titanium in this non-chromium surface treatment solution converted to SiO and TiO is 9

twenty two

It is 5% by weight, and the content ratio of titanium to the total amount of silicon and titanium is 4.8 atomic%.

[0103] Next, this non-chromium antifouling surface treatment agent was applied to five M8 bolts galvanized in a zincate bath by the dip-and-spin method, dried and held at 100 ° C for 20 minutes for baking. As a result of investigating crack resistance and anti-fouling performance for these bolts in the same manner as in Example 1, as shown in Table 2-2, almost all of the forces that were slightly inferior to Example 11 were obtained. It was good.

[0104] Example 13

52. Using 8 parts by weight of the alkoxysilane oligomer solution H, the TOG was reduced to 3.2 parts by weight compared to Example 11, and the non-chromium antifouling surface treatment of Example 13 with the composition shown in Table 2-2. An agent was prepared. The silicon and titanium in this non-chromium surface treatment solution are mixed with

The total content of C 2 and T 2 converted to 2 2 was 11.0% by weight, and the content of titanium with respect to the total content of C and T was 2.7 atomic%.

[0105] Next !, this non-chromium antifouling surface treatment was applied by dip-and-spin to the surface of 5 M8 bolts galvanized in a zincate bath, dried and kept at 100 ° C for 20 minutes and baked . These bolts were examined for crack resistance and fender resistance as in Example 1. As a result, as shown in Table 2-2, the amount of the titanium octylene glycol chelate compound was less than that of the non-chromium antifouling surface treatment agent of Example 11, and the antifouling performance was slightly inferior. Both It was almost good.

[0106] Example 14

52. TC-200 of titanium octylene glycol chelate compound in 8 parts by weight of alkoxysilane oligomer solution H (compound having an alkoxy group of n-otatoxide manufactured by Matsumoto Fine Chemical Co., Ltd. ) Was blended with 7.6 parts by weight, and the non-chromium antifouling surface treating agent of Example 14 was prepared with the composition shown in Table 2-2. The total content of silicon and titanium in the solution of this non-chromium surface treatment agent converted to SiO and TiO.

twenty two

Was 11.3% by weight, and the content ratio of titanium to the total amount of silicon and titanium was 4.6 atomic%.

[0107] Next, the non-chromium surface treatment solution was applied to five M8 bolts zinc-plated in a zincate bath by the dip-and-spin method, dried and held at 100 ° C for 20 minutes for baking. These bolts were examined for crack resistance and antifouling performance in the same manner as in Example 1. As shown in Table 2-2, the alkoxide groups of the titanium octylene glycol chelate compounds were different. Therefore, the anti-fouling performance was slightly inferior to that of Example 11, but almost good results were obtained.

[0108] Example 15

52. Titanium chelate obtained by chelating about half of the isopropoxy group of titanium tetraisopropoxide by adding 2 moles of acetylethylacetone to 1 mole of titanium tetraisopropoxide in 8 parts by weight of alkoxysilane oligomer solution H Compound TC-100 (product of Matsumoto Fine Chemical Co., Ltd.) was blended to obtain a non-chromium surface treating agent solution of Example 15 shown in Table 2-2. The silicon and titanium in this non-chromium surface treatment solution were converted to SiO and TiO.

2 2 The total content of silicon and titanium was 11.6% by weight, and the content of titanium with respect to the total content of silicon and titanium was 6.1 atom%.

[0109] Next, this non-chromium antifouling surface treatment agent was applied by dipping and spinning to the surface of five M8 bolts that had been galvanized in a zincate bath, dried and held at 100 ° C for 20 minutes for baking. As in Example 1, the crack resistance and the antifouling performance were examined. As shown in Table 2-2, the force that was slightly inferior to that of Example 11 was almost good. It was.

[0110] Example 16

In 45.9 parts by weight of alkoxysilane oligomer solution H, TOG and high boiling alcohol The non-chrome anti-mold surface treatment agent of Example 16 described in Table 2-2 was prepared by blending both PGME and ethylcetone solve. The total content of silicon and titanium in the solution of this non-chromium antifouling surface treatment agent converted to SiO and TiO is 9.9% by weight,

twenty two

The content ratio of titanium to the total amount of silicon and titanium was 4.6 atomic%.

[0111] Next, this non-chromium antifouling surface treatment agent was applied to five M8 bolts zinc-plated in a zincate bath by a dip-and-spin method, dried and held at 100 ° C for 20 minutes for baking. As a result of examining the crack resistance and the anti-fouling performance of these bolts in the same manner as in Example 1, as shown in Table 2-2, the force that was slightly inferior to that in Example 11 was almost the same. It was good.

[0112] Example 17

The non-chromium anti-surface treatment agent of Example 17 described in Table 2-2 was prepared by blending 52.8 parts by weight of the alkoxysilane oligomer j with TOG, PGME, which is a high boiling point alcohol, and ethyl acetate sorb. Prepared. The total content of kaen and titanium in the solution of this non-chromium anti-fouling surface treatment agent converted to SiO and TiO is 11.1% by weight.

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The titanium content relative to the total amount of titanium was 4.7 atomic%.

[0113] Next, this non-chromium antifouling surface treatment agent was applied to five M8 bolts zinc-plated in a zincate bath by the dip-and-spin method, dried and held at 100 ° C for 20 minutes for baking. As in Example 1, these bolts were examined for crack resistance and antifouling performance.

As shown in 2-2, good results were obtained.

[0114] Example 18

Tog was added to 73.4 parts by weight of the alkoxysilane oligomer solution H to prepare the non-chromium antifouling surface treatment agent of Example 18 shown in Table 2-2. The total content of keye and titanium in the solution of this non-chromium antifouling surface treatment agent converted to SiO and TiO is 1

twenty two

8. It was 9% by weight, and the content ratio of titanium with respect to the total amount of silicon and titanium was 4.6 atomic%.

[0115] Next, this non-chromium antifouling surface treatment agent was applied to five M8 bolts zinc-plated in a zincate bath by a dip-and-spin method, dried and held at 100 ° C for 20 minutes for baking. As in Example 1, these bolts were examined for crack resistance and antifouling performance. As shown in 2-2, the force, which was slightly inferior to that of Example 11, was almost satisfactory.

[0116] Example 19

The non-chromium surface treating agent of Example 19 shown in Table 2-2 was prepared by blending 45.9 parts by weight of the alkoxysilane oligomer solution H with TOG, PGME, which is a high boiling point alcohol, and ETB. The silicon and titanium in the solution of this non-chromium anti-fouling surface treatment agent are combined with SiO and TiO.

The total content of C and T in terms of 2 is 6.6% by weight, and the total content of C and T

2

The titanium content was 4.6 atomic%.

[0117] Next, this non-chromium antifouling surface treatment agent was applied to five M8 bolts zinc-plated in a zincate bath by a dip-and-spin method, dried and held at 100 ° C for 20 minutes for baking. As a result of examining the crack resistance and the anti-fouling performance of these bolts in the same manner as in Example 1, as shown in Table 2-2, the force that was slightly inferior to that in Example 11 was almost the same. It was good.

[0118] The titanium chelate compounds used in Examples 11 to 19 are commercially available products in which half of the alkoxy groups of titanium tetraalkoxide are blocked with a chelating agent.

[0119] [Table 2-1]

¾:-[[2210120-

O0.6wt% boric acid solution: 0.6wt% boric acid isopropyl alcohol

OPGME: Propylene glycol monomethyl ether

Oethyl solvate: Ethylene glycol monoethyl ether

01.2wt% boric acid solution: 1.2w «Boric acid in isopropyl alcohol

OTOG: Titanium glycol glycolate compound manufactured by Nippon Soda Co., Ltd. (purity 72%, alkoxy group is isopropoxy group)

◦TC-200: Titanium octylene glycol chelate compound manufactured by Matsumoto Fine Chemical Co., Ltd. (purity 67%, alkoxy group is n-octoxy group)

OTC-100: A compound obtained by chelating 2 moles of acetylylacetone with 2 moles of acetyl chloride from Matsumoto Fine Chemical Co., Ltd.

Alkoxysilane oligomer solution G in polybutylbutyral succinate solvate solution, epoxy-functional silane coupling agent γ-glycidoxypropyltrimethoxysilane, titanium oxide ultrafine powder slurry dispersed with bead mill ( A non-chromium anti-fouling surface treatment agent of Comparative Example 1 was prepared with the composition shown in Table 3 by blending ethyl acetate and titanium oxide (containing 5: 1 ratio). The content of silicon in this non-chromium surface treatment solution converted to SiO was 10.6% by weight. Then as in Example 1

2

Then, this anti-bacterial surface treatment agent was applied to the surface of five M8 bolts galvanized in a zincate bath by the dip-and-spin method, dried and held at 100 ° C. for 15 minutes for baking. These bolts were examined for crack resistance and anti-fouling performance in the same manner as in Example 1. As a result, there were few cracks in the anti-fouling film of the anti-fouling surface treatment after baking, and the salt spray tester It was taken out for 24 hours, and it was observed that a crack was formed in the fender film coated on the surface of the bolt that had been dried. In addition, as shown in Table 3, the antifouling performance evaluated in the salt spray test was inferior to the bolts applied with the non-chromium antifouling surface treatment agents of Examples 1 to 19.

[0122] Comparative Example 2

Using the alkoxysilane oligomer solution G containing no titanium component, dilute the alkoxysilane oligomer solution G with isopropyl alcohol, and apply the non-chromium antifouling surface treatment agent of Comparative Example 2 with the composition shown in Table 3. Prepared. The content of the kaen converted to SiO in the solution of the non-chromium surface treatment agent was 10.8% by weight.

2

[0123] Next, this anti-bacterial surface treatment agent was applied to five M8 bolts galvanized in a zincate bath by a dip-and-spin method, dried, held at 100 ° C for 20 minutes, and baked. As a result of examining the crack resistance and the anti-fouling performance in the same manner as in Example 1, as shown in Table 3, almost the same result as in Comparative Example 1 was obtained.

[0124] Comparative Example 3

Zirconium with 45.9 parts by weight of alkoxysilane oligomer solution H and 1 mol of zirconium tetra n-propoxide (ZA-40) manufactured by Matsumoto Fine Chemical Co., Ltd. reacted with 2 mol of 2-ethylhexanoic acid Kiretoi匕合was 8. 8 parts by weight, 10 weight ^_0/0 Echiruse port cellosolve solution of polyvinyl butyral, 0.6% isopropyl alcohol solvent solution of boric acid, isopropyl alcohol, PGME, and Table 3 the ETB Mix ratio with the formulation composition described in The non-chromium antifouling surface treatment agent of Comparative Example 3 was prepared. Incorporation of Ce and Zr in the solution of this non-chromium anti-fouling surface treatment agent converted to SiO and ZrO

twenty two

The amount is 11. a 2 wt ^_0/0, the content of zirconium to the total amount of Kei element and zirconium was 8.9 atomic%.

[0125] Next, this anti-bacterial surface treatment agent was applied to five M8 bolts zinc-plated in a zincate bath by the dip-and-spin method, dried and held at 100 ° C for 20 minutes for baking. As shown in Table 3, the crack resistance and the antifouling performance were examined in the same manner as in Example 1. As shown in Table 3, the occurrence of cracks was slight and the antifouling performance was relatively good. It was a little inferior to the bolt applied with the non-chromium antifouling surface treatment agent of Example 16 in which the compound was mixed. In addition, since the zirconium chelate compound is more expensive than the titanium chelate compound, the surface treatment cost is high and it is not practical.

[0126] [Table 3]

(For titanium dioxide fine powder, use Super Titania F-6 from Showa Denko KK)

0 Zirconium chelate compound: A liquid obtained by adding 2 moles of 2-ethylhexanoic acid to 1 mole of ZA-40 (zirconium tetra n-propoxide) manufactured by Matsumoto Fine Chemical Co., Ltd. It contains 30 wt% zirconium.

Claims

The scope of the claims

[1] Alkoxysilane oligomer alcohol solution having a weight average molecular weight of 1,000 to 10,000, wherein some of the silicon atoms in the alkoxysilane oligomer molecule are replaced with titanium having an organic chelate titanium compound power. The alcohol solution contains 2.5 to 15 atomic% of titanium with respect to the total amount of silicon and titanium, and the total amount of silicon and titanium in the alcohol solution contains each of the silicon and titanium. 5-20 when converted to SiO and TiO

twenty two

A non-chromium antifouling surface treating agent for metal members having a zinc surface that is wt%.

[2] Alcohol solution power of the alkoxysilane oligomer The hydrolyzate of the alkoxysilane raw material and the organic chelate titanium compound is obtained by adding an acid catalyst and water to an alcohol solution containing the alkoxysilane raw material and the organic chelate titanium compound. 2. The non-chromium antifouling surface treatment agent for metal members having a zinc surface according to claim 1, wherein the surface treatment agent is produced by condensation polymerization.

[3] The non-chromium antibacterial surface treatment for metal parts having a zinc surface according to claim 2, wherein the organic chelate titanium compound is obtained by blocking or replacing 40 to 60% of an alkoxy group of a titanium alkoxide with a chelating agent. Agent.

[4] The alkoxy 90-99 mole ^_0/0 of the silane material is smaller than the tetraalkoxysilane monomer or 8 00, a tetraalkoxysilane oligomer having a weight average molecular weight, the balance being alkylalkoxysilane monomer in claim 2 A non-chromium antifouling surface treating agent for metal members having the zinc surface described.

[5] The alkylalkoxysilane monomer is at least one selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. A non-chromium antifouling surface treatment agent for metal members having the zinc surface described in 1.

6. The non-chromium anti-mold surface treating agent for metal members having a zinc surface according to claim 3, wherein the chelating agent is β-diketone or octylene glycol.

[7] Alcohol solution power of alkoxysilane oligomer The alkoxysilane raw material is synthesized by synthesizing an alkoxysilane oligomer by hydrolyzing and polycondensing the alkoxysilane raw material by adding an acid catalyst and water to an alcohol solution containing the alkoxysilane raw material. 2. The silane-born ligoma mixed with an organic chelate titanium compound in an alcohol solution. A non-chromium antifouling surface treatment agent for metal members having a zinc surface.

8. The non-chromium antibacterial surface treatment for metal parts having a zinc surface according to claim 7, wherein the organic chelate titanium compound is obtained by blocking or replacing 40-60% of the alkoxy group of the titanium alkoxide with a chelating agent. Agent.

[9] The alkoxy 90-99 moles of silane material ^_0/0 tetraalkoxysilane monomer or 8

The non-chromium antifouling surface treating agent for metal members having a zinc surface according to claim 7, which is a tetraalkoxysilane oligomer having a weight average molecular weight smaller than 00 and the balance being an alkylalkoxysilane monomer.

10. The alkylalkoxysilane monomer is at least one selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. A non-chromium antifouling surface treatment agent for metal members having the zinc surface described in 1.

[11] The non-chromium antifouling surface treating agent for metal members having a zinc surface according to [8], wherein the chelating agent is β-diketone or octylene glycol.

[12] Alcohol solution power of alkoxysilane oligomers

The non-chromium antifouling surface treatment agent for metal members having a zinc surface according to claim 1, comprising 1 to 2% by weight.

13. The non-chromium antifouling surface treatment agent for metal members having a zinc surface according to claim 12, wherein the alcohol-soluble rosin is polyvinyl butyral.

[14] The alcohol solution of the alkoxysilane oligomer contains boric acid in an amount of 0.004 to 0.10 wt.

13. The non-chromium antifouling surface treatment agent for metal members having a zinc surface according to claim 12, wherein the surface treatment agent contains zinc.

15. The non-chromium for metal parts having a zinc surface according to claim 1, wherein 20 to 40% by weight of the alcohol component of the alkoxysilane oligomer in the alcohol solution is alcohol or glycol ether having a boiling point of 97 ° C. or higher. Antifouling surface treatment agent.

[16] Alcohol or glycol ether having a boiling point of 97 ° C or higher n-propyl alcohol mononole, n-butino enore eno oleore, propylene glycol eno mono mono eno enoenore, ethylene gnole konole mono eno eno enoenore and ethylene From Glicono Letter Shary Buchinore Etenore 16. The non-chrome anti-mold surface treatment agent for metal members having a zinc surface according to claim 15, which is at least one selected.

[17] A metal member having a zinc surface coated with a siliceous film having an average thickness of 0.5 to 3 μm formed of the non-chromium antifouling surface treatment agent according to claim 1.

18. The metal member having a zinc surface according to claim 17, wherein the siliceous film is applied by a dip and spin method.

[19] The metal member having a zinc surface according to [17], wherein the siliceous film is baked at a temperature of 120 ° C. or lower.